Molecular modeling of [VO(L1-4)(R)] complexes (R = bipyridine, phenanthroline): DFT study of antioxidant activity, DNA binding and evaluation of electron-donating and -withdrawing substituent groups.

A DFT (density functional theory) study was conducted with eight oxovanadium complexes (C1 - C8) of general formula [VO(L1-4)(R)] (R = bipyridine, phenanthroline; L1-4 = group of ligands derived from dithiocarbamate). The obtained geometries showed a good correlation with the experimental structures. Molecular orbital analysis revealed that the contribution of the L-ligand in the SOMO (single-occupied molecular orbital) of the complexes correlated with the experimental antioxidant activity (IC50), while the contribution of the R-ligand to the LUMO (lowest unoccupied molecular orbital) of the complexes correlated with the experimental complex-DNA interaction (Kb). It has been identified that the presence of an electron-donating substituent group (such as -NH2) in the C5 - C6 structures should enhance these complexes' antioxidant and DNA interaction activities.